PT97361A - FLAME DELAY PROCESS OF A FIBROUS ORGANIC SUBSTRATE CONTAINING REACTIVE GROUPS USING ANOTHER POLYMER CONTAINING NITROGEN - Google Patents

Description

72 428 Η 1015 2-

The present invention relates to a method of treating fabrics, in particular, to a process for rendering flame retardant fabrics by using organophosphorus compounds'

In US Pat. Nos. 2983623, 4068026, 4078101, 4145463 and 4494951 the flame retardant treatment of cotton fabrics is described with tetrakis (hydroxymethyl) phosphonium (hereinafter referred to as THP compounds) compounds or their -corporated with urea. The processes involved the impregnation of the fabric with an aqueous solution of the chemicals followed by drying, treatment with ammonia to cure the phosphorus compounds in order to insolubilize the phosphor in the fabric, finally oxidation and washing to obtain a treated fabric cusia flame resistance remains, even after many washes.

However, curing efficiency, which is a measure of the efficacy, of curing the insolubilization of phosphorus in the tissue, is not always ideal and a percentage of the expensive phosphorus chemicals applied in the impregnation step is not cured and is removed by washing the tissue, after curing, and wasted. The curing efficiency for cotton fabrics is greater than for cotton-polyester fabrics and especially for polyester-cotton fabrics, and in some cases with THP compounds, fire retardant properties can not be conferred, the latter type of fabric. In addition, although some techniques allow the necessary flame retardant properties to be imparted to the fabric when first cured, such properties often decrease significantly after repeated washing. The process of the present invention may increase the amount of the P-compound attached to the substrate, especially with substrates comprising non-cellulosic fibers, and may impart suitable fire retardant properties to fabrics comprising non-cellulosic fibers such as cotton-polyester blends. The present invention provides a process for flame retardant treatment of an organic fibrous substrate containing reactive groups which comprises impregnating said substrate with a nitrogen-containing polymer (or a precursor thereof) and a solution aqueous solution of an organophosphorus compound to provide an impregnated substrate which is dried and cured to provide a cured substrate. The nitrogen containing polymer may be applied to the substrate at the same time as the organophosphorus compound, but preferably the polymer, or precursor thereof, is applied in a first step to obtain a first impregnated substrate, and then the organophosphorus compound in a second step. The first impregnated substrate is usually allowed to stand to allow interaction of the polymer with the substrate prior to the second step.

Preferably, the nitrogen-containing polymer is free of phosphorus atoms and may be capable of reacting with cellulose by heating, e.g., by heating to 40 ° C. The polymer is preferably a polyelectrolyte containing a plurality of N atoms (especially in the tertiary or quaternary form), which may interrupt a polymer chain of carbon but which are preferably in pendant groups of a hydrocarbon polymer chain. The hydrophilic polymer backbone is preferably comprised of structural units derived from mono- or di-ethylenically unsaturated compounds containing one or more N-atoms. Examples of mono-ethylenically unsaturated compounds include vinyl compounds having a (Such as N-vinylpyridine, N-vinylpyrrolidine, N-vinylpyrrolidone and its ring C-alkyl derivatives) and also acrylic and methacrylic compounds with amide or amine groups such as acrylamide, methacrylate, acrylate and ammonium methacrylate, and the mono, di, and tri derivatives thereof. or tetra N-alkyl, especially those in which the alkyl group contains 1-6 carbon atoms (such as methyl or ethyl). The polymer may be a bromine or copolymer of monomers, each containing the atom, or atoms, of N, R 72 428 Η 1015

'" n-f'

Or may be a copolymer with other N-ethylenically unsaturated monomers, such as acrylic or methacrylic acid, or the corresponding esters, p ', with alkanols having 1-6 carbon atoms-A The proportion by weight of N-containing monomers to N-free monomers is usually 50-100: 50-0 (bp, 70-90: 30-10), but especially 80-100: 20 Examples of the diethylenically unsaturated compounds include diallylamines, especially diallylamine quaternized (such as N, N-dialkyl-N, N-diallylammonium halides) in which each alkyl group it contains 1-6 carbon atoms, such as ethyl, isopropyl, propyl or butyl, but especially methyl. Examples of copolymers include acrylic and acrylamide copolymers, acrylamide and dialkyl diallyl ammonium chloride, chlorides of polymeric dialkyldiallylammoniums may be those described in U.S. Patent No. 3,427,240, the disclosure of which is incorporated herein by reference. On the other hand, polymers of ethylenically unsaturated compounds may be prepared by conventional means, such as free radical polymerization, especially in an aqueous solution or in an aqueous emulsion. The nitrogen-containing polymer may also contain the atom of N in the polymer backbone and may be prepared by polymerization involving a ring-opening operation (such as in the known polymerization of ethylene-imine to obtain polyethylene-imine). The average molecular weight of the nitrogen-containing polymer is , usually 10000 - 5 million (ppm), 100000-3 million), and is soluble in water, (pg, with a solubility in water at 20 ° C of at least 10 g / l) or dispersible in water

Other nitrogen-containing polymers which may be used include water-soluble or water-dispersible polymers prepared by condensation polymerization and which are capable of still condensing with cellulose such as polyamines, polyamides and f

72 428 Η 1015 -5-polyamine / polyamide reaction products with epichlorohydrin

A precursor capable of forming the nitrogen-containing polymer by heating, in particular, a monomer which can be polymerized to form the polymer, eg, in situ in the tissue, during a drying or during the rest period, may be used. after one step, either after two impregnation steps, or between impregnations, in a two step impregnation (as hereinbefore described), or especially during any heat cure. Particularly useful ionizers are the diethylenically unsaturated compounds, such as the diallylamino salts mentioned above. The monomer may also be reacted with the substrate or the organophosphorus compound instead of polymerizing to form the polymer which then interacts. Preferably, the precursor is added in a separate first step from the organophosphorus treatment. The organic fibrous substrate is especially one which comprises or consists essentially of cellulosic fibers. The cellulosic fibers are preferably natural cotton fibers, but may be rami, flax, paper or paperboard, or regenerated fibers (eg, cupramonium or viscose fibers) or partially etherified or esterified cellulose (eg, cellulose acetate or propionate) . The substrate may be substantially fully cellulosic, e.g., 100% cotton, or may contain cellulosic fibers and non-cellulosic organic fibers, or may contain only non-cellulosic organic fibers, e.g., 100% polyester fibers. Usually, inorganic fibers, such as glass fiber, are absent.

The non-cellulosic fibers are preferably polyester or polyamide fibers, but may also be acrylic. The polyamide may be aliphatic, such as copolymers of a polyamine (such as a diamine), preferably an alkylenodia-mine, eg, 4-12 carbon atoms, and a polycarboxylic acid, eg an acid -amide, with 4-14 β atoms 72 428 Η 1015

carbon, such as an alkylenedicarboxylic acid (eg Nylon 66), or polylactams such as Nylon 6. Alternatively, the polyamide may be aromatic, such as aramides based on aromatic dicarboxylic acids and phenylenediamines. The acrylic polymer may be the homopolymer polyacrylonitrile or copolymer with vinyl chloride, as in modacrylic fibers. The substrate may contain at least 20% cellulosic fibers and up to 80% comestible fibers, eg, 80-80%, especially 25-80% co-mixable fibers such as polyamides. However, the substrate preferably comprises cellulosic fibers and polyester fibers. Usually, the substrate contains up to 80% (up to 70%) of polyester fibers and up to 20% (eg, - 30%) or more of cellulosic fibers, p and e, 1-80% or 1-70%, such as 15-70%, particularly, 22-38% or 45-75% polyester fibers and 20-99% or 30-99% (such as 30-85%), particularly, 62 -78% or 25-55% of cellulosic fibers.

Substrates comprising at least 45% non-cellulosic fibers, eg, polyester fibers, such as 45-100% polyester, are preferred, as are substrates comprising 30-78% cellulosic fibers and 22-70% fibers of polyester, or 30-62% of cellulosic fibers and 38-70% of polyester-polyester fibers is usually a condensation product containing structural units of an aliphatic alcohol, eg, a dihydric alcohol, especially ethylene glycol or butanediol (or mixtures thereof) and an aromatic dicarboxylic acid, eg, terephthalic acid, or a mixture thereof with other dicyclohexylic acids, such as isophthalic acid or sebacic acid.

If desired, the fibrous substrate may be one of the foregoing non-cellulosic substrates having groups capable of interacting with the cationic compound. Thus, the substrate may be a polyester, with the cationic polymer interacted with hydroxyl groups, or a polyamide, with the cationic polymer with a carboxyl or a polyacrylonitrile, with the cationic polymer having the nitride-polyester groups may be as described above, whereas the polyamide may be a reaction product of a polyamine, for example a diamine, eg, with a polycarboxylic acid, eg, a dicarboxylic acid of 4-14 carbon atoms. The polyacrylonitrile may be a homopolymer or a copolymer with vinyl chloride as in the modacrylic fibers .

The substrate fibers may be in the form of yarn or nonwoven fabric, but preferably are in the form of woven fabric. Blends of fibers, eg, cellulosic fibers and other fibers, may be an intimate or non-intimate blend, but the fibers are preferably in the form of a blend of cellulosic fibers and other fibers, eg, polyester fibers, such as in co-spun blends such as cut cotton-polyester or polyester-cotton fibers, but may be in the form of woven core yarn with a core of the other fiber, eg, polyester sheathed in cotton fibers. In one fabric the warp and weft fibers are preferably the same but may be different, e.g., one may be of cotton fibers and the other, e.g. of polyester cotton fibers. Thus, in the present description, the term " blend " also includes unions and unions / blends, as well as coated core fibers. Preferably, the substrate is a fabric having a weight of 0.05-1.0 kg / m 2 (eg, 0.150-0.40 kg / m 2) or 0.05-0.20 kg / m 2, such as a fabric of polyester-cotton for shirts, sheets or curtains. The nitrogen-containing polymer (or precursor thereof) is usually applied in the form of an aqueous solution or dispersion eg 0.1-30% (such as 0.2-15%), especially 0.5 -4% w / w for a pH of 2-9, bp, 2-4. The weight of nitrogen (or precursor) -containing polymer applied is usually 0.01-20% (eg, 0.1-10%), especially 0.5-5% based on the weight of non-woven fabric. treated. The nitrogen-containing polymer (or the precursor) may be impregnated into the fabric with a moisture retention of 50-150% and then, after initial drying, if desired (eg, with the impregnated fabric heated at 80-100 ° C for 0.1-5 minutes), the fabric is then treated by heating at 90-150øC (bp, 90-130øC) for 0.5-10 minutes (bp, 1-5 minutes). Instead of the heating step, the impregnated fabric may be maintained, e.g., at room temperature for 10-60 hours (bp, 10-30 hours) preferably 72 428 H 1015

'11'

If desired, the polymer (or precursor thereof) may be applied with a minimal addition addition technique to achieve a moisture retention of 10-50%; then the fabric may be dried or maintained with a residence time of pâ,,â, ..., 0.2-24 hours before the second step. A foam technique may be used for addition of a minimal addition with a forming agent cationic or amphoteric foam. It is believed that in this treatment or attachment step, the nitrogen-containing polymer interacts with the substrate, especially with the hydroxyl, abutting or ester groups of the substrate, to obtain a treated substrate having a cationic polymer attached or attracted to the substrate by ionic bonds

In the preferred form of the process, after treatment with the nitrogen-containing polymer, the substantially dry substrate is then treated with the organophosphorus compound. In the tetrakis (hydroxyorgano) phosphonium compound, each hydroxyorganic group is preferably an alpha- hydroxiorgano group having 1-9 carbons. Especially, said alpha- (hydroxyorgano) group has the formula wherein each of R1 and R2 (which may be the same or different) represents hydrogen or a Preferably, R 1 is hydrogen and R 2 is methyl or especially hydrogen, such as in tetrakis (hydroxymethyl) phosphonium (THP) compounds. The use of the tetrakis (tetrakis) hydroxiorgano) phosphonium bromide in general will hereinafter be exemplified with respect to the THP compounds with the corresponding molar amounts of the other compounds used instead of the THP compound. The substrate is treated with an impregnation solution which and is an aqueous solution of the THP salt mixed with a nitrogen compound condensable thereto to form a water-soluble precondensate, or a solution of a precondensate of said salt and the nitrogen compound, or a solution of the salt of THP, or a water-soluble self-condensate, or the at least partially neutralized THP salt (eg, THP hydroxide), with or without the nitrogen compound. Alternatively, the impregnation solution may comprise a solution of the aforementioned precondensate.

72 428 Η 1015 composed of nitrogen (eg urea), such as in a solution C with a mole ratio of total (free and combined) nitrogen compound to THP group (free and combined) of 0.8-2: 1, 0.8-1.5: 1. The nitrogen compound is preferably one having at least two NH groups (such as 2-4), but advantageously contains two NH groups or especially two NH 2 groups. The nitrogen compound is usually bifunctional and may be an amine , but is especially an amide. Examples of suitable nitrogen compounds include biuret, guanidine, melamine and methylolated melamines, but urea is the preferred species for the purposes of the present invention, especially in the absence of melamine or a methylolated melamine. The nitrogen compound is preferably urea where it is present in the precondensate.

In a preferred embodiment of the invention, the solution contains a precondensate of the THP salt, eg, the chloride or the sulfate, and the nitrogen compound, in a mole ratio of nitrogen compound to THP of 0.05-0.8: 1, eg, 0.05-0.6: 1, or 0.22-0.8: 1, such as 0.25-0.6: 1, especially 0.4-0.6: 1. The pH of said solution is usually 2-7.5, such as 4-6.5, b.p., 4-5. The atomic ratio of total N atoms in the nitrogen compound, or in the condensate, to the total P atoms in the THP salt, or in the condensate, in the impregnation solution is usually not more than 4: 1, bp, 1 -3: 1. The concentration of the organophosphorus compound in the aqueous solution may be 5-70%, e.g., 5-35% or 35-70% (by weight, with the THP + ion), but is preferably 20-35%. by weight.

If desired, the solution may contain a wetting agent, such as a nonionic wetting agent, eg, in an amount of 0.05-0.5% by weight of the impregnation solution, a fabric softener such as a fabric softener. polyethylene and in a preferred amount of 0.1-2% by weight and a salt of a strong acid and a weak base (such as ammonium or alkaline earth metal chloride or nitrate, or ammonium acid phosphate) as catalyst for heat curing, and in an amount of 0.1-5%, 72 428 Η 1015

-10-

The treated substrate is impregnated so as to have an organophosphorus retention of less than 40%, e.g., 10-40% (such as, 10-30%), especially, 20-30% (as THP based on the original weight of the substrate). The substrate may be impregnated with solution and the wet substrate, p "e", the fabric is usually squeezed to a moisture retention of 50-130%, eg, 60-100% Alternatively, the treated substrate may be impregnated with a concentrated impregnation solution by a technique of addition of a minimum addition, eg, a foam technique, and with a retention humidity of 10-50%. The organophosphorus impregnated substrate is then dried, eg, to a moisture content of 0-20%, eg, 5-15% such as about 10%, for subsequent curing with ammonia, substantially to dryness for curing by subsequent heat (the percentage being derived from the increase in the weight of the fabric and the weight of the impregnated chemicals). The drying can be carried out in a frame oven or on heated tubes, eg steam tubes, and may involve heating to 80-160 ° C for 10 minutes to 10 seconds, e.g., 100-120 ° C for 3 minutes to 30 seconds. The dried substrate is then cured. The cure may be effected by treatment with ammonia, usually gaseous ammonia, which diffuses through the substrate and / or is forced through the substrate, eg, by passing the fabric over a perforated tube through which ammonia is emitted. Examples of suitable apparatus and techniques for curing with ammonia are described herein and the disclosure of which is incorporated herein by reference. U.S. Patent No. 4,145,463, U.S. Patent 4,494,801 and U.S. Patent 4,494,951, the disclosures of which are hereby incorporated by reference. Alternatively, or preferably prior to curing with ammonia, the dried organophosphorus impregnated substrate can be heat cured, eg, at a temperature of at least 100 ° C (such as 100-200 ° C) or 100-180 (Such as 130-170 ° C) for 10 - 0.5 minutes, eg for 7-1 minutes.

Higher temperatures, with longer curing times, will be avoided with substrates containing at least a majority of cellulosic fibers, especially 100% cotton. 72 428

Η 1015 11 ί

While the dried substrate can then be cured with heat, preferably the drying and heat curing steps are simply combined by heating in the heat-curing conditions. When heat-cured fabric is desired to be subsequently , the heat cured fabric is preferably subjected to a moisture-balancing step to allow the fabric to recover its moisture content prior to treatment with ammonia.

Usually, the cured substrate has an add-on of solids (resulting from the organophosphorus impregnation and cure steps) of 10-50%, or 10-40%, (eg, 10-30%) as such as 10-25% or 15-30%, especially 20-30% (by weight, based on the original substrate), based on a total retention of organophosphorus compound of 16-36% eg 20-28% ( expressed as THP ion on the same basis) -

Usually, the cured substrate is then sampled at at least one of the following steps: further insolubilization of the cured resin in the treated substrate, oxidation in order to convert at least some of the trivalent phosphorus into penta-tavalent phosphorus on the cured resin, or aqueous based wash and washing with water. Preferably the oxidation is effected by contacting with an aqueous solution of an oxidizing agent, preferably a peroxide compound, such as an aqueous solution of hydrogen peroxide, eg, at a concentration of 0.5-15%, such as 1- 5%, or with a solution of sodium perborate, eg, at a concentration of .1-10%, usually applied in excess, and usually for 0.1-1 minutes at 0-40 ° C. Alternatively, the oxidation may be carried out with a gas containing molecular oxygen, preferably mercury, air, and particularly with the gas being drained or blown through the substrate. Thus, the substrate may be passed in the form of fabric, onto a vacuum slit or a perforated tube through which the gas is blown or drawn.

After oxidation, or in place of the oxidation, the cured substrate may be washed with an aqueous medium, preferably with a 72 428 → 1015

J

12- / /.....'-i > / tu ......., ·. &Amp; * ίϋ 4 * < &';' " aqueous base solution, b.p., a sodium carbonate solution, and / or rinsed with water. Preferably, the oxidation reduces the residual content of formaldehyde on the cured substrate.

Alternatively the cured substrate may be simply rinsed with water or subjected to other operations to reduce its content of water soluble materials. Finally, the cured fabric is dried to obtain a final substrate. The final substrate, eg, the fabric, can be used to manufacture work clothes such as overalls, overalls, and protective clothing, including uniforms, particularly 30-70%, eg, with 55-70% cotton and 70-30 %, eg, 45-30% polyester, and household fabrics such as sheets and curtains, particularly 30-70% cotton, 30-60% cotton and 40-70% polyester.

If the process of the invention is compared to the corresponding process without the step with nitrogen-containing polymer (or its precursor), the initial incorporation of THP compound by the substrate into the impregnation can be increased, curing efficiency can be increased and the loss of cured P compound from the final substrate during the washes can be reduced. Thus, for a constant total weight of phosphorus chemical applied to the substrate, the cured substrate of the invention usually has a higher percentage of phosphorus and can also have a better handling than the corresponding cured substrate without the initial treatment with the nitrogen containing polymer. There is thus less waste of phosphorus chemical. The flame retardant properties, eg, singleness, are usually improved allowing the fabrics to undergo more demanding flammability tests than without treatment with the nitrogen-containing polymer (or its precursor ). The final substrate obtained by the process of the invention may also have sufficient, cured and bound phosphorus-containing resin to enable it to meet the stringent flame retardant standards e.g. BS6249 Part 1 1984 Index B, which may not be

(Or precursor) thereof. The final substrate obtained by the process of the invention may also have a lower reduction of strength compared to the corresponding substrates without the initial treatment .

In this description, unless otherwise indicated, the parts and percentages are by weight. The invention is illustrated in the following Examples in which all the tissues were prevented undergoing a disengage treatment.

Example ..... 1.

An aqueous dispersion of poly (dimethyl diallylammonium chloride) was obtained by reaction in a reactor with stirrer and condenser, to which was added toluene (50 g) and a nonionic surfactant (15 g) and which was heated to Followed by the simultaneous addition of an aqueous solution of dimethyldiallylammonium chloride (50 g) in water (50 g) and di- (4-tert-butylcyclohexyl) peroxydicarbonate (0.15 g). The contents of the reactor were stirred at 80 ° C for 3 hours to give an emulsion which was then heated to remove toluene by distillation with water, with addition of more water to compensate for distilled toluene and water. was a stable, aqueous dispersion of polymer having an average molecular weight of about 1 million. (a) A 67:33 intimate blend of 0.246 kg / m 2 polyester cotton was impregnated with a 2% w / w aqueous dispersion of the above polymeric dimethyldiallylammonium chloride-excess liquid was then separated from the tissue which was allowed to dry at room temperature overnight to yield a treated tissue comprising about 1.6% of the polymer. (b) The treated tissue was then impregnated with an aqueous solution of a 1: 2 molar condensate of urea and tetrakis (hydroxymethyl) phosphonium chloride containing 25.2% solids (by weight, 72 428 Η 1015 -14- Λ, expressed as o ΤΗΡ), and m solid excess of the tissue.

(c) The fabric was then heat-cured at 150 ° C for 3 minutes and then the water content returned to normal by equilibration in a controlled humidity space overnight. The heat-cured fabric was then further cured with gaseous ammonia which was passed through the fabric in a chamber, as described in U.S. Patent 4,145,463. (d) After curing with ammonia, the fabric was washed with a 10% hydrogen peroxide solution, rinsed with water, washed with aqueous sodium carbonate, and then rinsed again and dried, yielding a final fabric

The final fabric was then analyzed for P and N contents, the flame retardant properties before and after washing were also tested 40 times at 93Â ° C, washing as described in procedure 1, DIN 53920 with soft water. The test method used was in accordance with Test 2A, B8 5438 (1989). In all cases the fabrics met the flammability requirements of BS 6249 Index B. The results of the analyzes were as follows:

FABRIC% of P% of N

Cured (step c) 1.94 1.56

Final fabric (step d) 1.81 1.65 The fabric passed the ignition test even after 40 washes. Example ..... 2.

The procedure of Example 1 was repeated with a different fabric, inter alia with a 60:40 cotton / polyester intimate blend fabric having a weight of 0.268 kg / ml, and a different pretreatment agent, namely with monomeric diallyldi-monoglydial chloride added in the form of an aqueous solution in concentrations of 2%, 5% or 10% in order to obtain a moisture retention of about 70- 90%. The analyzes of flammability,% of P and% of N, in the final tissue, as such, and after 20 washes were carried out. The results were as follows; (Mm) 2 3.05 3.05 60 2.63 2.40 50 5 2.9 (g) (g) (g) (g) (g) 2.90 5 4 2.43 2.24 47 10 2.98 2.90 58 2.38 2.19 42

Exemples .... 3 ... -... 9

The procedure of Example 1 was repeated with two different polymeric nitrogen compounds, namely (Examples 3-6) a water soluble copolymer of acrylamide and acrylic acid in a ratio of about 90:10 and (Examples 7 -9) a water-soluble polyethyleneimine. The final tissues and tissues were tested after 20 washes for flammability. All fabrics passed the flammability tests and the final fabrics were the following. results of these Example% of polymer in solution in step (a) Searing length (mm) 3 1 81 4 2 76 5 5 79 6 10 75 7 0.5 90 8 1.5 85 9 2 87

Claims (1)

72 428 Η 1015 -16 CLAIMS. A flame retarding process of a fibrous organic substrate containing reactive groups, characterized in that it comprises: a) impregnating the substrate with a nitrogen-containing polymer or a precursor thereof and with an aqueous solution of an organophosphorus compound; b) drying the substrate; c) curing the substrate by heating to a temperature of at least 100 ° C and / or treatment with ammonia. 2ã. A process according to claim 1, characterized in that the organophosphorus compound is applied to the substantially dry substrate after impregnation with the nitrogen containing polymer or its precursor. 3i. Process according to claim 1 or 2, characterized in that the fibrous organic substrate consists essentially of cellulosic fibers, for example natural cotton fibers, ramie, linen, cardboard, viscose or cupramonium, or acetate or propionate. 4ã. Method according to claim 1 or 2, characterized in that the fibrous organic substrate comprises cellulosic and non-cellulosic fibers, for example polyester, polyamide or polyacrylonitrile fibers. 5i. Method according to Claim 1 or 2, characterized in that the fibrous organic substrate consists essentially of non-cellulosic fibers. 6ã. A process as claimed in any one of claims 1 to 5, wherein said nitrogen-containing polymer is a polyelectrolyte, homopolymer or copolymer, containing a. which may interrupt a polymer chain of carbon or which may be pendant groups of a hydrocarbon polymer chain, especially when said nitrogen-containing polymer is free of phosphorus atoms, especially when said The nitrogen-containing polymer comprises a hydrocarbon polymer backbone comprising itself structural units derived from mono-hetylenically unsaturated compounds containing one or more N atoms, for example N-vinyl pyridine, N-vinylpyrrolidone, N-vinylpyrrolidone and their derivatives of C alquilo-alkyl of the ring, or acrylamide, methacrylamide, ammonium acrylate and methacrylate, their mono, di, tri or tetra N-methyl or N-ethyl derivatives, or structured units, derived from diethylenically unsaturated compounds containing one or more N, especially when said diethylenically unsaturated compounds are quaternized dialkylamine, wherein each alkyl group contains 1 to 6 carbon atoms, especially when said nitrogen-containing polymer is a dialkyl diallyl ammonium chloride homopolymer or a copolymer of acrylamide and dialkyl diallyl ammonium chloride. 7ã. Process according to any of claims 1 to 5, characterized in that the nitrogen-containing polymer comprises a hydrocarbon polymer backbone, also comprising, in itself, nitrogen-free ethylenically unsaturated monomers, for example acrylic or methacrylic acid or the corresponding esters with alkanols of 1-6 carbon atoms, especially when the weight ratio of nitrogen-containing monomers to nitrogen-free monomers in said nitrogen-containing polymer is from 50: 50 to 100: 0, especially when said ratio , by weight, is from 80:20 to 100: 0, especially when said nitrogen-containing polymer is a copolymer of acrylic acid and acrylamide. A process according to any one of claims 1 to 5, wherein the nitrogen-containing polymer also contains the nitrogen atom in the backbone of the polymer, for example when said nitrogen-containing polymer is polyethylene. 4 72 428 Η 1015 9a. Process according to any one of claims 1 to 5, characterized in that the nitrogen-containing polymer is formed by condensation polymerization and in that said nitrogen-containing polymer is capable of being further condensed with cellulose, for example when said nitrogen-containing polymer is a polyamine, polyamide or a polyamine / polyamide reaction product with epichlorohydrin. A process according to any one of claims 1 to 9, characterized in that the nitrogen-containing polymer has an average molecular weight of from 1000 to 5 million, in that said nitrogen-containing polymer is soluble in water or dispersible in water, said nitrogen-containing polymer, or a precursor thereof, is applied to the substrate in the impregnation (a) thereof, in the form of an aqueous solution or dispersion, especially when the concentration of said aqueous solution or dispersion is 0.1 to 30% w / w, and the weight of nitrogen-containing polymer or its precursor thus applied is 0.01 to 20% based on the weight of the untreated fabric. llã. A process according to any of claims 1 to 10, characterized in that the impregnation (a) is carried out by treating said substrate with a solution comprising a nitrogen-containing polymer, or a precursor thereof, for example a diallylamine salt, so that the retention of moisture is 50 to 150% especially when the impregnated substrate is then subjected to one or more of the following treatments: (i) drying by heating at a temperature of 80 to 100 ° C for 0.1 to 5 minutes, (ii) heating at a temperature of 90 to 150Â ° C for 0.5 to 10 minutes, (iii) maintaining at room temperature for 10 to 60 hours especially when said impregnated substrate is allowed to dry concurrently. 12§. Method according to any of claims 1 to 72 428 Η 1015 -19-10, characterized in that the nitrogen-containing polymer, or precursor thereof, for example a diallylamine salt, is applied to the substrate in the impregnation (a) thereof by a final addition technique especially when the minimal build up technique is a foaming technique, using a cationic or amphoteric foam forming agent, and a stabilizer, and in that the moisture retention is 10 to 50%. 13ã. A process according to any one of claims 1 to 12, characterized in that the impregnation (a) is carried out with a tetrakis (hydroxyorganos) phosphonium compound, especially when said hydroxyorganic group is an alpha-hydroxyorganic group having 1 to 9 carbons, especially when said alpha-hydroxyorganic group has the general formula HO-CHR 2 R 3 in which R 1 and R 2, which are the same or different, are hydrogen or an alkyl group having 1 to 4 carbons, especially a compound of tetrakis (hydroxymethyl) phosphonium (THP), or a water-soluble self-condensate, or a water-soluble condensate thereof, with an organic nitrogen compound, for example urea, biuret, guanidine, melamine or methylamine or a mixture of said organic nitrogen compound with the phosphonium compound or a condensed or self-condensed compound thereof. 14i. A process according to any one of claims 1 to 13, characterized in that the impregnation (a) is carried out using a solution comprising a pre-condensate of THP salt and the organic nitrogen compound, such that the molar ratio of organic nitrogen compound to THP is between 0.05: 1 and 0.8: 1, especially between 0.25: 1 and 0.6: 1, especially between 0.4: 1 and 0.6: 1, in that said solution has a pH of 2 to 7.5, especially 4 to 5, and in that the concentration of the organophosphorus compound (by weight, expressed as THP + ion) in said impregnation solution is 5 to 70% said impregnation solution also comprising a or more of the following additives: (i) a wetting agent, especially when said wetting agent is non-ionic and especially when said wetting agent is present in an amount of from 0.05 to 0.5% by weight of said impregnation solution; (ii) a fabric softener, especially when the fabric softener is present in an amount of 0.1 to 2% by weight, of said impregnation solution; (iii) a catalyst, especially when said catalyst comprising a salt. of a strong acid and a weak base, for example an alkaline earth metal or ammonium chloride or nitrate, or an ammonium acid phosphate, and especially when said catalyst is present in an amount of 0.1 to 5%, in The method of any one of claims 1 to 14, wherein the impregnation (a) is carried out by treating said substrate with said impregnation solution, so as to obtain a retention of organophosphorus of less than 40% (expressed as THP + ion, based on the original weight of said substrate) especially 20 to 30% (expressed as THP + ion, based on the original weight of said substrate). A method according to claim 15, characterized in that the wet substrate is squeezed to a moisture retention of 50 to 130% (by weight, based on the original weight of said substrate). of Claims 1 to 14, characterized in that the treated substrate is impregnated with a concentrated impregnation solution by means of a minimum build technique, in particular by a foaming technique, and in that the moisture retention is 10 to 50% ( by weight, based on the original weight of said substrate). A process according to any one of claims 1 to 17, characterized in that the heating curing of (c) is carried out in a stenter or a baking oven at a temperature of from 100 to 180 ° C and the cure time is from 10 to 0.5 microliters to 72 428 to 1015 to 19%. A process according to claim 18, characterized in that said heating curing is carried out before curing with ammonia. A process according to any one of claims 1 to 19, characterized in that the cured substrate is subjected to least one of the following operations: (i) further insolubilization of the cured resin in the treated substrate; (ii) oxidation; (iii) washing with an aqueous base and washing with water; in that the oxidation (ii) is carried out by applying an excess oxidizing agent for 0.1 to 10 minutes at a temperature of 0 to 40 ° C, in that said oxidizing agent is an aqueous solution of hydrogen peroxide with a concentration of 0.5 to 15% w / w or an aqueous solution of sodium perborate having a concentration of 1 to 10% w / w or by subjecting the cured substrate to oxidation by means of a gas containing molecular oxygen , which is drained or blown through the substrate. By ALBRIGHT & WILSON LIMITED - 0 OFFICIAL AGENT -